Process of refining hydrocarbon oils



May 20, 1930. E. w. GARD ET AL y 1,759,7

PROCESS 0F BEFINING HYDROCARBON OILS J JC k w la N'J LL u i LA napPatented May 20, 1930 EARLE W. GARD, BLAIR G. .ALLRIDC-tE, `HUGH J.MULTER, AND RAYMOND T. HOWES,

OF LOS ANGELES COUNTY, CALIFORNIA PROCESS OF REFINING YDROCARBON OILSApplication filed September 12, 1927. Serial No. 219,147.

This invention relates to a methodof treat-` ing petroleum oildistillates, and While not necessarily confined thereto, it morespecilicall rela-tes to the treatment of gasoline or iitha stocksderived by distillation of crude petroleum oil, or syntheticall Yproduced from any of the Well-known crac ing operations. This inventionis a continuation in part of the applications of Earle W. Gard, BlairGr.

Aldridge and Hugh J. Multer, Serial Numbers 148,730, 148,731 and 148,732filed November 16, 1926. In these pendingr applications an apparatus andprocess is disclosed for the Vseparation of water and also for thesepara tion of sulfuric acid reaction products from petroleum oilscontaining the same.

We have discovered an additional lmprovement to the process of theseapplications, by'

means of which a more complete separation of the oil from the separatedproducts of emulsion 0r suspension may be made. This improvementconsists in continuously returning to the filter medium which may beforaminous plates or any other filter medium containing capillarypassages, that part of the separated products of emulsion or suspensionwhich contains oil. We have determined that in order to obtain acomplete separation of the oil from the products of emulsion, such 30 asWater or acid-sludge, in our filter separaf tor, it may be necessary toreturn a certain percentage of oil along with the products of emulsionseparated in the last compartment or last two compartments of the filterseparator, which are returned back to the system, to be again passedthrough the filter se arator, thereby making a substantially comp eteseparation of the oil from the undesired products of emulsion which areeliminated continuously from the separator by the draw-ofi' pipes of theother compartments.

Vith the foregoing preliminary explanation the preferred form of ourinvention Will now be more fully explained by reference to theaccompanying drawings, which are diagrammatical representations ofapparatuses, in which the invention may be performed. In Figure 1 of thedrawings there is shown a complete apparatus for refining naphtha,gasoline, or lamp oil stocks. Figures 2, 3 and 4 show various forms offilters that may be employed.

In Figure l, 1 represents generally a tank for holding the naplitha orcrude gasoline to be treated. A pipe 2 is connected to the crudegasoline tank 1 at the bottom-controlled b Y a valve 3. The pipe 2 isconnected to the branch pipe 4, controlled by a valve 5 and leading tothe suction side of pump (3J A pipe 7, controlled by a valve 8, connectsthe discharge side of pump 6 to the inlet side of the foraminous platedehydrator 9, in which 10 represents the foraminouslilter plates.

119 represents the draw-cti' pipes from the foraminous plate dehydrator`9 controlled by the valves 120. The said draw-ofi' pipes 119are'connected to a pipe 121 which is connected to a tank 122. 72 is arecirculating pipe controlled by the valve 73, and connected to the pipe4 leading toV the suction side of the pump 6. pipe 11 is connected tothe foraminous plate dehydrator 9 and leads to a jet mixer 12. The jetmixer 12 is connected to a sulfuric acid storage tank 74 by pipe 75 andcontrolled by valve 7 G. the jet mixer 12 to a branch pipe 13. Thebranch pipe 13, controlled by a valve 14 is connected to settling tank15 near the top. The settling tank 15 is connected to a second, settlingtank 17 by the pipe 16. A pipe 18 is connected to the top of settlingtank 17 and leads to branch pipes 19 and 29.

Branch pipe 19 is connected to sludge separator 20. Sludge separator 20is provided at the bottom With six dravveotl' pipes 81 controlled by sixvalves 82. The draw-o pipes 81 are all connected to a pipe 83, which isconnected to settling'tank 17 at the bottom by pipe 79 controlled byvalve 80. The pipe 83 also is connected to settling tank 15 by the pipes78 controlled by the valve 77. A branch pipe 84 controlled by a valve 85is connected to the pipe 83 and leads to a source not shown. Therecirculating pipes 22 and 23 controlled by valves 24 and 25 arcconnected to pipo 26, leading to the suction side of pump 27. The pump27 discharges through pipe 28 into the ranch pipes 29 and 30, which arecontrolled by valves 31 and Pipe 30 is connected Pi e 12 connects pipe29 is connected through pipe 19 to the sludge se arator 20. Thesludgeseparator is-'plrovi ed with a plurality of oraminous plates 21. A pipe33 connects the sludge separator 2O to a branch pipe 34 and 36controlled by the valves 35 and 37. The branch pipe 34 is connected to aclay mixer tank-38.- The branch pipe 36 is connected to a; pipe 52 whichin turn is connected to a pipe .53. The clay mixer 38 is provided with aclay elevator 87, having a clay bin 86 and discharging through a chute88. A Iiipe 39,'controlled by the va ve 40, connects the cla mixer 38 tothe suction side of T e pump 41 discharges into pipe 42''fciitrolledbyvalve 42 and connected to a settling tank 43.V A branch piie 90,controlled byvalve 90', connects the ischarge of pump 41 tothe bottom ofthe cla mixer 38. A pipe 89'connects settling tan .43 to pipe 91 and 92controlled by valves 93 and 92. Pipe 92fis'connected through pipe-90 tothe clay mixer 38. Pipe 91 leads toa centrifuge 94. The centrifugeV 94is providedwith an outlet 95, which disn charges into a cla bin 96. Apipe 44 is connected to the setting tank 43 at the top and is connected'to a branch pipe 45 and 46 controlled by valve 45 and 51. Pipe 45 isconnected Y to filter press 47 vcontaining filter so leaves 481eadin tooutlet pipe 49, controlled by valve 50; ipe 49 being connected by .pipe52 to pipe53. Pipe 46 is connected by pipe `52 to pipe 53. The ipev53 is'connected Y to a jet mixer 54 'to whic .is connected pipe "sa 102controlled by valve '103, connected Vto a settling tank 64. A'fpipe 55connects the dis'- charge side of the et mixer 43-to a settling tank 56.The sett 'ng tank 56 is provide with a draw-off ipe 104 controlled by avalve 105, this draw-o pipe leading to a source not shown. The settlingtank 56is connected by a pipe 57 to a jet mixer 58 which discharges intopipe-59 leading to a settlin tank 60. The )et mixer 58 is also connecteto a pipe 107 which is connected to aV tank '106 and controlled by avalve 108. Y The settling tankV v 60 is provided with a draw-o pipe 109con-V 1 4 trolled by a valve 110 and leads to a source not n I:y shown.'The settling tank 60 is Vconnected to Lio-a thirdV jet mixer 62 by` pipe61. lThe said controlledby a valve 101, which in turn is connected to acaustic tank 99. il The et mixer 62 dischar s into' aY ipe 63, lvvhic 56Ynectedto e said sett ing tank 64. The set-- tling tank 64 is connectedat the top bya.' pipe65, Vwhich leads to a settling tank 66.`Ay

The settling tank 66 is provided witha draw o ipe 113 controlled by avalve 114. The 60 a water spray 112, which Vis connected to a pipe 111which leadsto a source of water not shown. The settling tank 66 isconnected Y to settling tank 68 by the pi 67. The set-4 tling tank 68 isprovided wit a water Vspray Vfurie ac i Ajet mixer 62 is alsoconnectedto a'pipe 100 Y is con-v 7 The acid treated gasoline."I

sett ing tank 66 is provided at the top with 116 which is connected to apipe 115 and leads to a source of Water not shown. The said settlingtank 68 is connected to a finished gasoline tank 71 by the Ypipe v69 andcontrolled by the valve 70.

The preferred process as carriedvout with the apparatus described is `asfollows:

Gasoline or naphtha stock, stored in tank 1, to be treated, isdischarged by pump 6 through the dehydrator 9 passing through the pipe 7controlled by the valve 8. The dehydratorl 9 is provided with a numberof foraminous plates 10, by means of which the water contained inthercrude gasoline stocks is separated in stages, duringthe passagethrough the plates and isrdrawn oi at the end of each stage ofseparation into tank 122,

Vthe flow ofY separated material being regulated by valves '120, so thatsubstantially none of the gasoline stocks pass into this tank 122.

The Vfinal separation of` the water from the crude gasoline is attainedafter the passage of the oil through the last foraniinous plate, theseparated Water being drawn off through the line 72 controlled by thevalve 73 along with a certain small percentage of crude gasoline stock,and recirculated in order to separate the water completely. This watercontaining a small amount of gasoline stock,

drawn oil' fromtheflast compartment of the dehydrator 9, flows into thesuction side of the pump 6 and is-again passed through the dehydrator 9valong with other stock ycoming from the crude gasolinetank 1, whereby adehydrated crude gasoline stock flows Vfrom the outletof the dehydrator49 and passes into the jet mixer 12, whereit receives a flow of 'sul-pfurie acid coming from the tank'74 through the ipe 75 controlled by thevalve 76.

T e quantityV of sulfuric aci l introduced is regulated in proportiontothe lamount necessary to treat the gasoline stock to the required jdegree of color and purity and may be varied from Yas Vlow as 1A, poundtoas,l highas 15 z pounds per barrel of gasoline stock treated,

or more, depending upon theV stock treated and the clarity desire In theet mixer 12 the gasoline and sulv are commingled and lthendischargedinto a settling tank 15, .passing through the pi r13controlled by lthe valve andare drawn olf through the pipes 78, 83

and 84 controlledv by the valves 77 Vand 85,

iis

' 1'4. In the sett ing tank y15 the acid products of reactionsettle fromthe treated gasoline ond settling tank 17 ,where more of the acid-`sludge settles out and in like manner drawn .n voff at the bottom,passing into the pipes 83 and 84, controlled by the valves 80 and 85,the pipe 84 leading to a storage for acid-v sludge not shown. From thesettling tank 17 the treated gasoline stock passes into the sludgeseparator 20 Where the balance of the acid-sludge or products of thesulfuric acld treatment are substantially completely Vseparated from thetreated gasoline which is accomplished by passingV through theforaminous plates 21, which agglomerate the suspended acid-sludge andcauses thesame to settle to the bottom of the various compartments, fromwhich it is drawn ott through the draw-oli pipes 81 controlled by theValves 82, that substantially no gasoline passes into the pipe 83. Acomplete separat-ion of the acid-sludge is obtained in the last twoVcompartments of the sludge separator and is drawnV off along with asmall percentage of the gasoline stock through the pipes 22 and 23controlled by the Valves 24 and 25, this flow being recirculated andregulated so that all the sludge is permitted to flow out ot thecompartment along with the small percentage of gasoline stock.

This acid sludge containing the small percentage of gasoline stock flowsinto the suction side of the recirculating pump 27, which discharges thesaid products through pipe 28 back into the system, either at thesettling small portion of the stock tank 15, passing'through the pipe 30and 13 controlled by the valve 14, or at the inletof the sludgeseparator passing through pipe 29 controlled by Valve 31. The acidtreated gasoline free of acid reaction products passes from the sludgeseparator 20 through the pipe 33 into a clay mixer or treating tank 38,Where an adsorbent clay is commingled with the acid treated gasolinestock in quantities suiticient to purify and decolorize the gasolinestock to the required degree.

Thisoperationis accomplished by introducing a clarifying anddecolorizing clay into the clay mixer 38 through the conveyor 87 andchute 88, a circulating agitation being maintained by means of pump 41which takes suction on the gasoline stock contained in the clay mixerand discharges a portion of the samev through the pipe 90 and controlledby valve 90, and back into the bottom of the said clay mixer 38. Theclay treated lgasolinefstock contained in the clay mixer 38 iscontinuously discharged into a settling tank 43 by means of the pum 41passing through the pipe 42 controlled the valves 42', a beingdischarged back into the clay mixer 38 in order to keep the clay andAgasoline commin led. The treated gasoline stock and clay which iscontinuously discharged into settling tank 43, separate, the gasolinebeing drawn oit at the top Aflows through the pipe 44 and 45 and intothe filter press 47 where it iscompletely separated from any claykarticles, which may be carried along with t e gasoline stock.

The gasoline stock free of clay passes from Y the filter press 47 intothe pipe 49 controlled by valve 50 `and then into a jet mixer 54 Whereit is commingled with a once-used caustic soda solution, coming from thecaustic soda settling tank 64, passing through the pipe 102 controlledby the valve 103. The commingled gasoline stock and once-used. causticsoda solution are discharged into the settling tank 56, Where thegasoline stock separates from the used caustic soda solution and l'lowsinto a second jet mixer 58, passing through the pipe 57. VIn jet mixer58 the said' treated gasoline stock is commingled with a'water solutionof sodium hypochlo rite in quantities suicient to render the gasolinestock sweet to lthe doctor test. From jet mixer 58 the treated gasolinestock and sodium hypochlorite solution pass into the settling tank 60,where the gasoline separates from the sodium hypochlorite solution andflows into a third jet mixer 62, passing through the pipe 61. v L

In the jet mixer 62 the sodium hypochloritetreated gasoline stock iscommingled with a solution of caustic soda, coming from caustic sodastorage tank 99, passing through pipe 100 controlled by Valve 101. Thecommingled gasoline stock and caustic soda solution are discharged fromthe jet mixer 62 into a settling tank- 64 passing through the pipe 63.In the settling tank 64 the caustic treated gasoline stock separatesfrom the caustic soda solution and passes through the pipe 65 into thesettling tank 66 Where it is washed with a spray of Water coming from asource not shown, passing through the pipe 111 and being sprayed intothe tank through the jet openings112. 1

The gasoline 'stock passes from settling tank 66 into a second settlingtank 68 Where it is again Washed in like manner as before, Withawater'spray coming from a source not shown, passing through the pipe115 and out through the jet openings 116.

The gasoline stock, `which is 'now 4substantially free from allimpurities, passes from the settling tank 68 into the finished gasolinetank 71, through the pipe 69, controlled by the p'ipe 70. s

In the Washing operation of the gasoline stock ai'ter the treatment withcaustic soda, in settling tanks 66 and 68 the Water is continuouslydrawn oi, as it separates, through the pipes 113 and 11i"y controlled.by valves 114 and 118, to a source of Waste not shown. 4The usedv sodiumhypochlorite solution which separates in the settling tank 60 iscontinuously drawn ed, as it separates, through the pipe 109 controlledby the Valve 110 through a source not shown.

The used caustic soda solution which separates inthe settling tank 56 iscontinuously drawn off, as it separates, through the pipe 104 controlledbythe Valve 105 and is con ducted to a recovery plant not shown.

The decoloriziug clay is drawn ofi' from les Y -gasoline content, ma

the settling tank 43 continuously as it sepa-` rates and passes throughthe pipe, 89 and back into the clay mixer 38 where it is again Vusedalong with a new or unused decolorizing clay. However, a portion of thisused clay is continuously or intermittently drawn from the settling tank43 through the ipe 89 and 91 into the centrifuge 94,' contrdlled b the-valve 93.V In the centrifuge 94 the clay is completely separated fromthe gasoline stock, the gasoline stock bein conveyed back into thesettling tank 4 3, or t e settling tank 56, by a means not shown', to befurther treated for the production of finished as- 'oline-stock,v andthe clay, free of aso 'ne stock.

- It is tobe understood that any efficient filter medium lcontainingcapillar passages may be employed instead of a oraminous plate filter,such for example as glass wool, sand, steel Wool, wood pulp, and thelike.

While the process herein described is well adapted for carrying out theobject of the present invention, it is to be understood that variousmodifications and chan es may be made without departing from t e spiritvof the invention and the invention includes all such changes andmodifications as come within the scope of the appended claims.

What we claim is:

step Vin the process for separatingj products of emulsion from an'oil,comprising, continu-v ously passing an oil containing products ofemulsion through aseries of solid foraminous blocks containing capillarypassages toy ag glonierate the emulsified constituent contained in saidoil, causing said agglomerated constituents to separate from the oil instages, continuously removing that art of the agglomerated constituentswhich is. substantially free of oil, continuously re-passing that partof the constituents which isnot substantially free of oil again throughthe same series of solid foraminous blocks, alon with the said oilcontaining the products o emulsion to beagglomerated and separated instages.

2. In the refining of hydrocarbon oils, that step in the process forseparating products of emulsion comprising, continuously passing an oilcontaining products of emulsion through a plurality of spaced solidforarninous blocks containingy capillary passages, containing means forwithdrawing liquids own inthe art, or it between said solid foraminousblocks, ag-

glomerating the'emulsified constituents contained in said oil,.causingsaid ag lomerated constituents to separate from the oil in stages,

emulsion from an oil, comprising continuously'passing an oil'throughaplurality; of spaced solid foraminous blocks containing capillarypassages with means. for separating and withdrawing liquids between saidsolid foandremoving a portion ofthe emulsified constituentssubstantially free' of oil; agglomerating, separating and re-passingthe' other portion of ythe emulsified constituents containing oilthrough the same plurality of s aced solid foraminous blocks alon with esaid oil containing the products o emulsion -to be agglomerated andseparated in stages substantially as described. Y -V 4. A rocess ofrefining hydrocarbon oils comprising, first dehydrating said oil bypassing the same throu h a chamber containing a plurality'of spacefilter mediums containing capillary passages, with means for withdrawingliquids between said'filter mediums, agglomerating the emulsified Watercontained in the said oil, causingl said agglomerated water to separatefrom the oil in stages, removing'that part of the agglomerated waterwhich l. In the refining 'of hydrocarbon oils, that v is substantiallyfree of oil re-passing that part of the Waterwhich is not substantiallyfree of oil again throu h Vthe same series of spaced filter mediums aong with the said oil containing the water of emulsion to beagglomerated and se arated; commingling said dehydrated oil wit sulfuricacid in quantities suflicient to combine with `constituents to beseparated, settling and separating a part of the sulfuric acid with thecombined constituents, then passing the acid treated oil with theremaining part of the sulfuric acid and combined constituents though achamber containing a pluralityof spaced filter mediums containinglcapillary passages, with means for separating and withdrawing liquidsbetween said filter mediums; agglomerating, separating and removing aportion `of the acid constitu/ents substantially yfree of oil;agglomeratiug, separating and -re-passing the 'other portion of the acidconstituents containing oil,

through the saine plurality of spaced filter mediums along with tliesaid oil'containing the acid reaction products to be agglomerated andseparated vin stages; commingling the raminous blocks; agglomerating,separating .85'

acid treated oil substantially free of acid constituents withaclarifying and decolorizing agent, separating the clarifying anddecolor'- izing agent with the adsorbed constituents 5 from the clariedand decolorized oil; comming-ling the acid treated clarified anddecolorized oil with an agent capable of rendering the oil sweet to thedoctor test, separating the reagent employed for renderlng lo the oilsweet to the doctor test; commingling the thus treated oil with a Watersolution of caustic soda, separating the caustic soda from the treatedoil, and nally washing the thus treated oil with Water.

15 In testimony whereof We aiX our signa,-

tures.

EARLE W. GARD. BLAIR G. ALDRIDGE.

HUGH J. MULTER. 2Q RAYMOND T. HOWES.

